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WO2017163817A1 - Tôle métallique traitée en surface pour adhésion au moyen d'une résine à base de polyoléfine, et élément composite mettant en œuvre celle-ci - Google Patents

Tôle métallique traitée en surface pour adhésion au moyen d'une résine à base de polyoléfine, et élément composite mettant en œuvre celle-ci Download PDF

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Publication number
WO2017163817A1
WO2017163817A1 PCT/JP2017/008458 JP2017008458W WO2017163817A1 WO 2017163817 A1 WO2017163817 A1 WO 2017163817A1 JP 2017008458 W JP2017008458 W JP 2017008458W WO 2017163817 A1 WO2017163817 A1 WO 2017163817A1
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WO
WIPO (PCT)
Prior art keywords
acid
resin
chemical conversion
polyolefin resin
adhesive layer
Prior art date
Application number
PCT/JP2017/008458
Other languages
English (en)
Japanese (ja)
Inventor
康雄 平野
岳史 渡瀬
哲也 山本
Original Assignee
株式会社神戸製鋼所
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社神戸製鋼所 filed Critical 株式会社神戸製鋼所
Priority to EP17769862.8A priority Critical patent/EP3434470B1/fr
Priority to US16/081,493 priority patent/US11897230B2/en
Priority to CN201780014391.4A priority patent/CN108778716B/zh
Priority to KR1020187030396A priority patent/KR102142843B1/ko
Publication of WO2017163817A1 publication Critical patent/WO2017163817A1/fr

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    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B32B2323/10—Polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2419/00—Buildings or parts thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2479/00—Furniture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2509/00—Household appliances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C09J2400/16—Metal
    • C09J2400/163—Metal in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00—Presence of graft polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00—Presence of graft polymer
    • C09J2451/003—Presence of graft polymer in the primer coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

Definitions

  • the present invention relates to a polyolefin-based resin-treated surface-treated metal plate excellent in adhesiveness and a composite member using the same.
  • metal parts such as steel plates (metal plates) are used in automobiles, home appliances, office automation equipment, and the like. In many cases, such a metal part is used after a metal plate is press-molded and given a predetermined shape and then joined to another metal part or a plastic part by welding or screwing.
  • the adhesion of plastic to the surface of the metal plate can be imparted, after the metal plate is press-molded, it is set in a plastic mold, poured into molten plastic, and solidified by cooling.
  • a metal plate composite resin molded product (hereinafter referred to as a composite member) bonded to a resin molded product such as a plastic part can be formed, which leads to the efficiency of the member manufacturing process and the weight reduction of the member.
  • the present applicant is a surface-treated steel sheet in which a metal substrate, a chemical conversion treatment film, and an adhesive layer are laminated in this order.
  • a surface-treated steel sheet is proposed in which the treated film contains colloidal silica and a thermosetting resin.
  • Patent Document 1 a resin molded product containing a polypropylene resin is used.
  • the composite member obtained by bonding the surface-treated steel sheet of Patent Document 1 and a resin molded product containing polypropylene resin has a certain degree of adhesive strength between the metal substrate and the resin molded product (hereinafter, simply referred to as adhesive strength).
  • adhesive strength the degree of adhesive strength between the metal substrate and the resin molded product.
  • the resin contained in the chemical conversion film is a thermosetting resin, the chemical conversion film and the adhesive layer may be easily peeled off. That is, it may not be said that there is sufficient adhesion when used in applications where high adhesion is required, such as automobile structural parts.
  • Patent Document 1 also proposes a surface-treated steel sheet in which a primer layer is provided between the chemical conversion film and the adhesive layer to increase the adhesive strength, but the surface treatment is performed by laminating three layers on the metal substrate. It is necessary to produce a steel plate, which increases the number of manufacturing steps and increases the manufacturing cost. In addition, it is desired to reduce the number of stacked layers from the viewpoint of weight reduction of members that are required in recent years.
  • an object of the present invention is to provide a surface-treated metal sheet for bonding a polyolefin resin excellent in adhesiveness at a low cost.
  • One aspect of the present invention is a polyolefin-based resin-bonded surface-treated metal plate in which an adhesive layer is laminated on at least one surface of a metal substrate via a chemical conversion treatment film, the coating forming the chemical conversion treatment film.
  • the working solution contains an acid-modified polyolefin resin, colloidal silica, and a silane coupling agent, and the amount of the chemical conversion coating is 0.05 to 3 g / m 2 in terms of dry mass. It contains an acid-modified polyolefin resin, and the adhesive layer has a thickness of 5 to 100 ⁇ m.
  • the adhesive bond layer is laminated
  • the coating liquid for forming the chemical conversion film contains an acid-modified polyolefin resin, colloidal silica, and a silane coupling agent, and the amount of the chemical conversion film is 0.05 to 3 g / m 2 in terms of dry mass.
  • the adhesive layer contains an acid-modified polyolefin resin, and the thickness of the adhesive layer is 5 to 100 ⁇ m.
  • the surface treatment metal plate excellent in adhesiveness can be manufactured at low cost by using the chemical conversion treatment film containing acid-modified polyolefin resin and the adhesive bond layer containing acid-modified polyolefin resin.
  • the surface-treated metal plate of the present invention can be used for casings and interior / exterior parts of automobiles and household electric products, and for outer plate materials such as steel furniture and building materials.
  • the composite member of the present invention is useful for various applications such as automobile parts, home appliances, building materials, and OA equipment.
  • an adhesive layer is laminated on at least one surface of the metal substrate only through the chemical conversion treatment film.
  • Metal substrate (steel plate)
  • a metal substrate used by this invention for example, in addition to steel plates, such as a non-plated cold rolled steel plate, a hot dip galvanized steel plate, an alloyed hot dip galvanized steel plate, an electrogalvanized steel plate, an aluminum plate and a titanium plate Etc.
  • a hot dip galvanized steel plate, an electrogalvanized steel plate, an aluminum plate, and a titanium plate are preferable, and an alloyed hot dip galvanized steel plate is more preferable.
  • the thickness of the metal substrate is not particularly limited, but is preferably about 0.3 to 3.2 mm for reducing the weight of the final product.
  • various metal substrates can be used for this invention.
  • the chemical conversion treatment film can be prepared using a coating solution for forming a chemical conversion treatment film containing an acid-modified polyolefin resin, colloidal silica, and a silane coupling agent.
  • the coating liquid for forming a chemical conversion treatment film used in the present embodiment contains an acid-modified polyolefin resin, that is, the chemical conversion treatment film contains an acid-modified polyolefin resin.
  • the acid-modified polyolefin resin preferably includes an acid-modified polypropylene resin.
  • the acid-modified polyolefin resin used in the present embodiment is obtained by graft polymerization of at least one selected from the group consisting of unsaturated dicarboxylic acids, anhydrides thereof and ester derivatives onto the polyolefin resin.
  • the polyolefin resin used as a raw material for the acid-modified polyolefin resin examples include polyethylene, polypropylene, polybutene, polymethylpentene, ⁇ -olefin and ethylene or propylene copolymer, ethylene-vinyl acetate copolymer, ethylene- Resin such as acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-maleic anhydride copolymer, propylene-maleic anhydride copolymer, etc., may be used alone or in combination of two or more. It may be used. From the viewpoint of suppressing peeling between the chemical conversion film and the adhesive layer, the polyolefin resin preferably includes a polypropylene resin, and more preferably a polypropylene resin.
  • the polypropylene resin may be homopolypropylene (propylene homopolymer), which is a copolymer of propylene and one or more selected from the group consisting of ethylene, other ⁇ -olefins, and vinyl compounds. Also good.
  • Other ⁇ -olefins are preferably ⁇ -olefins having 4 to 18 carbon atoms, such as 1-butene, isobutene, 1-pentene, 4methyl-1-pentene, 1-hexene, 1-octene, 1-decene, -Dodecene and the like.
  • homopolypropylene is particularly preferable from the viewpoint of adhesion between the chemical conversion film and the adhesive layer.
  • Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.
  • Examples of the unsaturated dicarboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • Examples of the ester derivative of unsaturated dicarboxylic acid include monomethyl maleate. Of these, unsaturated dicarboxylic acid anhydrides are preferred, and maleic anhydride is more preferred.
  • the unsaturated dicarboxylic acid, anhydride or ester derivative thereof may be used alone or in combination of two or more.
  • the acid-modified polyolefin resin is produced by graft polymerization of unsaturated dicarboxylic acid, its anhydride or ester derivative to the above-mentioned polyolefin resin according to a conventional method.
  • a maleic anhydride-modified polyolefin resin can be synthesized as follows. Using xylene, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate as a solvent, polypropylene resin, maleic anhydride, and organic peroxides (eg, t-butylperoxy-2-ethylhexyl carbonate) ) In any order or together, and maleic anhydride-modified polyolefin resin is obtained by graft polymerization of maleic anhydride onto the polyolefin resin under normal heating, for example, at about 130 to 150 ° C. I can do it.
  • organic peroxides eg, t-butylperoxy-2-ethylhexyl carbonate
  • the acid value of the acid-modified polyolefin resin in the chemical conversion film is preferably 3 to 100 mgKOH / g, more preferably 5 to 80 mgKOH / g, and still more preferably 5 to 60 mKOH / g.
  • the acid value is less than 3 mgKOH / g, it is difficult to produce a water-based chemical conversion coating film-forming coating solution.
  • the graft amount of maleic anhydride in the acid-modified polyolefin resin is preferably 0.1 to 10% by mass, more preferably 0.3 to 7% by mass, and 0.5 to 5% by mass. More preferably. If the graft amount is less than 0.1% by mass, the adhesive strength may be insufficient. On the other hand, when the graft amount exceeds 10% by mass, the compatibility with the unmodified polyolefin resin may be deteriorated.
  • 2 or more types of unsaturated dicarboxylic acid, its anhydride, and ester derivative are used, let the sum of these content be graft amount.
  • the chemical conversion film preferably does not contain any thermoplastic resin other than the acid-modified polyolefin resin, but other thermoplastic resins other than the acid-modified polyolefin resin may be used as long as the effects of the present invention are not impaired. May be included.
  • thermoplastic resins include polystyrene resin, acrylonitrile-butadiene-styrene (ABS) copolymer, acrylonitrile-EPDM-styrene (AES) copolymer, acrylic resin, polybutadiene, polyacetal resin, polyether resin, Polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride and the like can be mentioned, and these may be used alone or in combination of two or more.
  • the content of the acid-modified polyolefin resin is preferably 80% by mass or more, more preferably 90% by mass or more, and 99.91% by mass or more. Is more preferably 99.95% by mass or more, and most preferably 100% by mass (the resin contained in the chemical conversion film is only an acid-modified polyolefin resin).
  • the thermoplastic resin is preferably 30 to 60 parts by mass, more preferably 35 to 55 parts by mass, and more preferably 40 to 50 parts by mass in 100 parts by mass of the solid content of the coating solution for forming a chemical conversion film. More preferably. Further, the thermoplastic resin contained in the chemical conversion coating is preferably 30 to 60% by mass, more preferably 35 to 55% by mass, and further preferably 40 to 50% by mass.
  • the coating liquid for forming a chemical conversion film preferably contains colloidal silica. That is, it is preferable that colloidal silica is contained in the chemical conversion treatment film of this embodiment. It is because it has the effect which improves corrosion resistance by including colloidal silica.
  • colloidal silica “XS”, “SS”, “40”, “N”, “UP”, etc. of “Snowtex (registered trademark)” series (colloidal silica manufactured by Nissan Chemical Industries, Ltd.) are preferably used. .
  • “Snowtex (registered trademark) 40” having a surface area average particle diameter of about 10 to 20 nm is preferably used.
  • the amount of colloidal silica is preferably 30 to 60 parts by mass, more preferably 35 to 55 parts by mass, and more preferably 40 to 50 parts by mass, based on 100 parts by mass of the solid content of the chemical conversion film forming coating solution. More preferably. Further, the amount of colloidal silica contained in the chemical conversion coating is preferably 50 to 150 parts by mass and preferably 75 to 125 parts by mass with respect to 100 parts by mass of the thermoplastic resin contained in the chemical conversion coating. More preferred.
  • the silane coupling agent is contained in the coating liquid for chemical conversion treatment film formation.
  • the adhesion of the chemical conversion film to the metal substrate can be improved.
  • the silane coupling agent include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ( amino group-containing silane coupling agents such as ⁇ -aminoethyl) - ⁇ -aminopropylmethyldimethoxysilane; ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -glycidoxypropyltri Glycidoxy group-containing silane coupling agents such as ethoxysilane and ⁇ -glycidoxy
  • silane coupling agents may be used alone or in combination of two or more.
  • an amino group-containing silane coupling agent and a glycidoxy group-containing silane coupling agent are preferable, and an amino group-containing silane coupling agent is more preferable.
  • the amount of the silane coupling agent is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, based on 100 parts by mass of the solid content of the chemical conversion film forming coating solution. More preferably, it is part by mass.
  • silane coupling agent for example, Shin-Etsu Silicone KBM903 (3-aminopropyltrimethoxysilane), Toray Dow Corning Z-6011 (3-aminopropyltriethoxysilane).
  • Z-6020 (3- (2-aminoethyl) aminopropyltrimethoxysilane) manufactured by Toray Dow Corning is preferably used.
  • the adhesion amount of the chemical conversion coating is 0.05 to 3 g / m 2 , preferably 0.1 to 2.5 g / m 2 , more preferably 0.2 to 2 g / m 2 in terms of dry mass. .
  • the adhesion amount of the chemical conversion coating is out of the above range, the adhesive strength with the resin molded product may be lowered.
  • a chemical conversion coating film is formed by applying a coating solution for forming a chemical conversion coating containing an acid-modified polyolefin resin, colloidal silica, and a silane coupling agent to at least one surface of the metal substrate.
  • a coating solution for forming a chemical conversion coating containing an acid-modified polyolefin resin, colloidal silica, and a silane coupling agent
  • other known additives may be added to the coating solution.
  • the method for forming the chemical conversion coating on the metal substrate is not particularly limited, and a conventionally known coating method can be employed.
  • a coating liquid for chemical conversion coating can be applied by a roll coater method, a spray method, a curtain flow coater method, or the like. It can be used by applying to one or both surfaces of the surface of the metal substrate and drying by heating.
  • the heating and drying temperature is not particularly limited, but since the coating liquid for forming the chemical conversion film is aqueous, it may be heated at around 100 ° C. where water evaporates for
  • An adhesive layer made of an adhesive containing an acid-modified polyolefin-based resin is provided on the chemical conversion film to obtain a surface-treated steel sheet.
  • the adhesive layer may be provided on the entire surface of the chemical conversion treatment film, or may be provided only on a part of the surface of the chemical conversion treatment film.
  • the adhesive layer may be provided in some lines or dots. Also good.
  • the adhesive layer those having excellent adhesiveness with a resin molded product to be described later combined with the surface-treated steel sheet are preferable.
  • the adhesive contains an acid-modified polyolefin resin, preferably an acid-modified polypropylene resin, and more preferably an acid-modified polypropylene resin.
  • the acid value of the acid-modified polyolefin resin in the adhesive layer is preferably 5 to 60 mgKOH / g, more preferably 10 to 50 mgKOH / g, and still more preferably 13 to 40 mgKOH / g. If the acid value of the acid-modified polyolefin resin is outside the above range, the adhesive strength may be lowered.
  • the acid-modified polyolefin resin can be produced by the same method as the acid-modified polyolefin resin contained in the chemical conversion film.
  • the acid-modified polyolefin resin contained in the adhesive layer may have the same or different acid value as the acid-modified polyolefin resin contained in the chemical conversion coating, but preferably has the same acid value. .
  • the adhesive layer preferably contains no thermoplastic resin other than the acid-modified polyolefin resin, but other thermoplastic resins other than the acid-modified polyolefin resin may be used as long as the effects of the present invention are not impaired. May be included.
  • thermoplastic resins include polystyrene resin, acrylonitrile-butadiene-styrene (ABS) copolymer, acrylonitrile-EPDM-styrene (AES) copolymer, acrylic resin, polybutadiene, polyacetal resin, polyether resin, Polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride and the like can be mentioned, and these may be used alone or in combination of two or more.
  • the content of the acid-modified polyolefin resin is preferably 80% by mass or more, more preferably 90% by mass or more, and 99.91% by mass or more. Is more preferably 99.95% by mass or more, and most preferably 100% by mass (the resin contained in the adhesive layer is only an acid-modified polyolefin resin).
  • the thickness of the adhesive layer after drying is 5 to 100 ⁇ m, and preferably 10 to 90 ⁇ m. If the thickness of the adhesive layer is out of the above range, the adhesive strength may be lowered.
  • a hot melt adhesive containing an acid-modified polyolefin-based resin is applied on the chemical conversion film to laminate an adhesive layer.
  • the hot melt adhesive can be applied by a known method, and for example, can be applied to the surface of the chemical conversion treated steel sheet in a powder state. Moreover, you may apply
  • the surface-treated steel sheet of this embodiment can be used in combination with a resin molded product (resin layer), that is, a composite member in which a resin layer is provided on an adhesive layer.
  • a resin molded product that is, a composite member in which a resin layer is provided on an adhesive layer.
  • an adhesive layer may be provided after press-forming the chemical conversion treated steel plate into a target shape, and a target shape of the surface treated steel plate provided with the adhesive layer on the chemical conversion treated steel plate You may press-mold. Then, the surface-treated steel sheet is inserted into a mold of an injection molding machine, clamped, and the molten resin is injected into the mold. When the resin is cooled and solidified, a composite member is obtained.
  • the surface-treated steel sheet of the present embodiment may be combined with the resin layer by a press molding method, but it is preferable to adopt the injection molding method in order to take advantage of the short time and high efficiency of the injection molding.
  • the injection molding conditions may be appropriately changed according to the type of resin constituting the molded product.
  • the resin molded product is a polypropylene resin
  • the cylinder temperature is 230 to 250 ° C. and the mold temperature is The temperature can be 45 to 55 ° C.
  • the injection holding time can be 5 to 8 seconds
  • the cooling time can be about 20 to 30 seconds.
  • the resin layer includes a polyolefin resin.
  • polyolefin resins include polyethylene, polypropylene, polybutene, polymethylpentene, copolymers of ⁇ -olefin and ethylene or propylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid. Examples thereof include resins such as acid copolymers, ethylene-maleic anhydride copolymers, and propylene-maleic anhydride copolymers, which may be used alone or in combination of two or more.
  • the polyolefin-based resin preferably includes a polypropylene resin, and more preferably includes only a polypropylene resin.
  • the resin layer may contain about 5 to 60% by mass of reinforcing fibers such as glass fibers and carbon fibers.
  • reinforcing fibers such as glass fibers and carbon fibers.
  • the adhesive strength of the composite member is preferably 12 MPa or more, more preferably 12.5 MPa or more, further preferably 13 MPa or more, and particularly preferably 14 MPa or more.
  • the adhesive strength of the composite member can be sufficiently increased even in the case of a surface-treated steel sheet having only two layers of a chemical conversion film and an adhesive layer on a metal substrate. A method for measuring the adhesive strength will be described later.
  • the present invention is a polyolefin-based resin-bonded surface-treated metal plate in which an adhesive layer is laminated on at least one surface of a metal substrate via a chemical conversion coating, and the coating liquid for forming the chemical conversion coating is ,
  • An acid-modified polyolefin resin, colloidal silica, and a silane coupling agent, and the amount of the chemical conversion film is 0.05 to 3 g / m 2 in dry mass
  • the adhesive layer is an acid-modified polyolefin.
  • a thickness of the adhesive layer is 5 to 100 ⁇ m.
  • the acid value of the acid-modified polyolefin resin in the chemical conversion coating is preferably 3 to 100 mgKOH / g, and the acid-modified polyolefin resin in the chemical conversion coating is It is preferable to include an acid-modified polypropylene resin.
  • the acid value of the acid-modified polyolefin resin in the adhesive layer is preferably 5 to 60 mgKOH / g, and the acid-modified polyolefin resin in the adhesive layer is It is preferable to include an acid-modified polypropylene resin.
  • the metal substrate is preferably a steel plate.
  • the present invention also includes a composite member in which a resin layer containing a polyolefin resin is provided on the adhesive layer in the surface-treated metal plate, and the polyolefin resin preferably contains a polypropylene resin. .
  • the present invention also includes a method for producing the surface-treated metal plate for bonding a polyolefin-based resin, which includes a chemical conversion treatment containing an acid-modified polyolefin-based resin, colloidal silica, and a silane coupling agent.
  • a step of laminating an adhesive layer is also includes a method for producing the surface-treated metal plate for bonding a polyolefin-based resin, which includes a chemical conversion treatment containing an acid-modified polyolefin-based resin, colloidal silica, and a silane coupling agent.
  • the longitudinal end portion of the surface-treated steel plate and the longitudinal end portion of the resin layer are gripped with a chuck of a tensile tester in an atmosphere at 25 ° C., and the tensile strength is 10 mm / min.
  • the tensile strength was measured when the resin layer was peeled off from the surface-treated steel sheet, and the value was taken as the adhesive strength.
  • the longitudinal end of the surface-treated steel sheet is the end that is not covered with the resin layer
  • the longitudinal end of the resin layer is the end of the surface-treated steel sheet that is not bonded. It is a part.
  • Example 1 [Preparation of maleic anhydride grafted polypropylene resin]
  • 400 ml of xylene and 60 g of granular homopolypropylene (melt flow rate: 4 g / 10 min) were placed, and the mixture was heated and stirred at 140 ° C. in a nitrogen stream.
  • 40 ml of xylene in which 11 g of maleic anhydride and 4 g of t-butylperoxy 2-ethylhexyl carbonate were dissolved was dropped into the stirred solution over 1 hour, and then the reaction was performed for 1 hour.
  • maleic anhydride grafted polypropylene resin The graft amount of maleic anhydride in the obtained maleic anhydride grafted polypropylene resin was 3.0% by mass, and the acid value of the obtained maleic anhydride grafted polypropylene resin was 25 mgKOH / g.
  • a stainless steel pressure vessel was charged with 10 g of the maleic anhydride grafted polypropylene resin, 1 g of triethylamine, 10 g of butanol and 30 g of distilled water, and stirred at 170 ° C. for 1 hour at 100 rpm. Thereafter, the mixture was cooled to obtain a maleic anhydride-grafted polypropylene resin aqueous dispersion.
  • Snowtex (registered trademark) 40 surface area average particle size: 10 to 20 nm) manufactured by Nissan Chemical Industries, Ltd. was used as colloidal silica
  • KBM903 ⁇ -aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd. was used as a silane coupling agent.
  • [Chemical conversion steel sheet] A coating solution for forming a chemical conversion film is applied to the surface of a galvannealed steel sheet having a thickness of 1.0 mm so as to have a dry mass of 0.2 g / m 2, and heated at 100 ° C. for 1 minute. The chemical conversion treatment steel plate provided with the processing film was obtained.
  • the surface of the surface-treated steel sheet is not adhered so as to be completely covered with the resin layer, and the resin layer and the surface-treated steel sheet overlap each other with a length of 12.5 mm ⁇ 25 mm (only part of the surface of the surface-treated steel sheet). Are covered with a resin layer) to obtain a composite member.
  • the injection conditions are shown in Table 2. Further, the adhesive strength of the composite member was measured by the above-described measuring method, and the results are shown in Table 1.
  • Example 2 and 3 Comparative Examples 1 and 2
  • a composite member was obtained in the same manner as in Example 1 except that the adhesion amount of the chemical conversion coating was changed to the amount shown in Table 1.
  • the adhesive strength of the composite member is shown in Table 1.
  • Example 4 Comparative Examples 3 to 4
  • Example 4 A composite member was obtained in the same manner as in Example 1 except that the thickness of the adhesive layer was as shown in Table 1.
  • the adhesive strength of the composite member is shown in Table 1.
  • Example 6 to 10 Comparative Examples 5 to 6
  • a composite member was obtained in the same manner as in Example 1 except that the maleic anhydride grafted polypropylene resin of the chemical conversion coating was changed to the acid values shown in Table 1.
  • the adhesive strength of the composite member is shown in Table 1.
  • the acid value of the resin was adjusted by adjusting the charging ratio of homopolypropylene and maleic anhydride.
  • Example 11 to 12 Comparative Examples 7 to 8
  • a composite member was obtained in the same manner as in Example 1 except that the maleic anhydride grafted polypropylene resin of the adhesive layer was changed to the acid values shown in Table 1.
  • the adhesive strength of the composite member is shown in Table 1.
  • the acid value of the resin was adjusted by adjusting the charging ratio of homopolypropylene and maleic anhydride.
  • the composite members provided with the surface-treated steel sheets of Examples 1 to 12 that satisfy the constituent requirements of the present invention were excellent in adhesive strength.
  • Comparative Example 3 since the adhesive layer was too thin, the composite member provided with the surface-treated steel sheet of Comparative Example 3 was inferior in adhesive strength. In Comparative Example 4, since the adhesive layer was too thick, the composite member provided with the surface-treated steel sheet of Comparative Example 4 was inferior in adhesive strength.
  • Comparative Example 5 since the acid value of the acid-modified polypropylene resin in the chemical conversion film was very small, it was not possible to produce a water-based chemical conversion film forming coating solution. In Comparative Example 6, an attempt was made to produce a resin having a very large acid value of the acid-modified polypropylene resin in the chemical conversion coating, but no acid-modified olefin resin could be produced.
  • Comparative Example 7 since the acid value of the acid-modified polyolefin resin in the adhesive layer was too low, the composite member provided with the surface-treated steel sheet of Comparative Example 7 was inferior in adhesive strength. In Comparative Example 8, since the acid value of the acid-modified polyolefin resin in the adhesive layer was too high, the composite member provided with the surface-treated steel sheet of Comparative Example 8 was inferior in adhesive strength. This is presumably because the adhesive force between the resin layer and the adhesive layer was weak.
  • the surface-treated steel sheets of Comparative Examples 9 to 10 have a chemical conversion film that does not contain an acid-modified polyolefin resin. Therefore, the composite members provided with the surface-treated steel sheets of Comparative Examples 9 to 10 were inferior in adhesive strength.
  • the present invention has wide industrial applicability in the technical field related to the surface-treated metal sheet.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Chemical Treatment Of Metals (AREA)

Abstract

L'invention concerne une tôle métallique traitée en surface pour adhésion au moyen d'une résine à base de polyoléfine dans laquelle une couche d'adhésif est stratifiée sur au moins une face d'un substrat métallique avec un revêtement par traitement chimique pour intermédiaire. Un liquide de revêtement formant ledit revêtement par traitement chimique comprend une résine à base de polyoléfine modifiée par un acide, une silice colloïdale et un agent adhésif au silane. La capacité de dépôt dudit revêtement par traitement chimique est comprise entre 0,05 et 3g/ｍ２ en termes de masse sèche. Ladite couche d'adhésif est caractéristique en ce qu'elle comprend une résine à base de polyoléfine modifiée par un acide, et en ce qu'elle présente une épaisseur comprise entre 5 et 100μｍ.
PCT/JP2017/008458 2016-03-25 2017-03-03 Tôle métallique traitée en surface pour adhésion au moyen d'une résine à base de polyoléfine, et élément composite mettant en œuvre celle-ci WO2017163817A1 (fr)

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EP17769862.8A EP3434470B1 (fr) 2016-03-25 2017-03-03 Tôle métallique traitée en surface pour adhésion au moyen d'une résine à base de polyoléfine, et élément composite mettant en ouvre celle-ci
US16/081,493 US11897230B2 (en) 2016-03-25 2017-03-03 Surface-treated metal plate for polyolefin resin bonding and composite member using same
CN201780014391.4A CN108778716B (zh) 2016-03-25 2017-03-03 聚烯烃系树脂粘接用表面处理金属板及使用其的复合构件
KR1020187030396A KR102142843B1 (ko) 2016-03-25 2017-03-03 폴리올레핀계 수지 접착용 표면 처리 금속판 및 그것을 이용한 복합 부재

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JP2016061676A JP6621694B2 (ja) 2016-03-25 2016-03-25 ポリオレフィン系樹脂接着用表面処理鋼板及びそれを用いた複合部材
JP2016-061676 2016-03-25

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11642871B2 (en) 2017-03-29 2023-05-09 Kobe Steel, Ltd. Surface-treated metal plate for polyolefin bonding, composite member, and method for manufacturing composite member
EP4035892A4 (fr) * 2019-09-26 2023-10-04 Toyobo Co., Ltd. Stratifié

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3063254B1 (fr) * 2017-02-27 2019-03-22 Saint-Gobain Glass France Procede d'encapsulation
JP6751041B2 (ja) 2017-03-17 2020-09-02 株式会社神戸製鋼所 ポリオレフィン接着用表面処理金属板、及び複合部材
JP7443019B2 (ja) * 2019-10-24 2024-03-05 株式会社放電精密加工研究所 水性プライマー処理組成物
JP7148021B1 (ja) * 2021-01-07 2022-10-05 日本製鉄株式会社 機器
CN113745719B (zh) * 2021-08-03 2022-12-16 嘉庚创新实验室 一种锂离子电池用钢塑膜及其制备方法
WO2023106239A1 (fr) * 2021-12-10 2023-06-15 ソニーグループ株式会社 Configuration adhésive, équipement électronique et procédé d'adhérence

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002212749A (ja) * 2001-01-19 2002-07-31 Nippon Steel Corp 耐プレスかじり性と耐コイル変形性に優れた非クロメート型表面処理金属板及びその製造方法
JP2015080884A (ja) * 2013-10-22 2015-04-27 日新製鋼株式会社 複合体およびその製造方法、ならびに塗装金属素形材およびその製造方法
WO2015064689A1 (fr) * 2013-10-31 2015-05-07 株式会社神戸製鋼所 Plaque métallique traitée en surface et article moulé composite de plaque métallique-résine

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20010053451A1 (en) * 2000-03-30 2001-12-20 Yoshiaki Togawa Laminated product and process for producing the same
DE10149148B4 (de) * 2000-10-11 2006-06-14 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen, Polymere enthaltenden Zusammensetzung, die wässerige Zusammensetzung und Verwendung der beschichteten Substrate
EP1599551B1 (fr) * 2003-02-25 2012-05-09 Chemetall GmbH Procede de revetement de surfaces metalliques au moyen d'une composition riche en polymeres
CN100509382C (zh) * 2005-09-01 2009-07-08 角正三郎 金属色泽装饰薄片、装饰金属板
US7476445B2 (en) * 2006-10-02 2009-01-13 Nippon Steel Corporation Surface-treated metal sheet
JP5323321B2 (ja) 2007-02-13 2013-10-23 ユーエムジー・エービーエス株式会社 水性分散体およびその製造方法
DE102007011553A1 (de) 2007-03-09 2008-09-11 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen, Polymere enthaltenden Zusammensetzung, die wässerige Zusammensetzung und Verwendung der beschichteten Substrate
JP2008266446A (ja) * 2007-04-19 2008-11-06 Unitika Ltd 水性コート剤および積層体
CN101396888B (zh) 2007-09-27 2013-01-09 比亚迪股份有限公司 一种金属复合板及其制备方法
JP5798312B2 (ja) * 2010-09-21 2015-10-21 倉敷紡績株式会社 一体押出成形体および建築用部材
US20150024215A1 (en) * 2012-03-27 2015-01-22 Mitsubishi Paper Mills Limited Silver-plated coated body
KR101654453B1 (ko) * 2012-05-21 2016-09-05 미쯔이가가꾸가부시끼가이샤 복합체 및 복합체의 제조 방법
JP5355803B1 (ja) * 2013-01-18 2013-11-27 日新製鋼株式会社 塗装金属素形材、複合体、およびそれらの製造方法
WO2014157289A1 (fr) * 2013-03-26 2014-10-02 日本軽金属株式会社 Corps lié métal/résine, et procédé de fabrication de celui-ci
JP2015196878A (ja) * 2014-04-01 2015-11-09 株式会社神戸製鋼所 表面処理鋼板および複合部材
EP3196266A4 (fr) * 2014-09-17 2018-05-02 DIC Corporation Adhésif pour stratifiés, empilement l'utilisant et batterie secondaire
US11104829B2 (en) * 2015-10-26 2021-08-31 Toyobo Co., Ltd. Adhesive composition and hot-melt adhesive
WO2017134931A1 (fr) * 2016-02-03 2017-08-10 昭和電工株式会社 Adhésif destiné à un stratifié de feuille métallique et film de résine, corps stratifié, matériau d'emballage d'extérieur de batterie, et boîtier de batterie et son procédé de fabrication
JP6705680B2 (ja) 2016-03-30 2020-06-03 株式会社神戸製鋼所 非縮合型熱可塑性樹脂接着用化成処理金属板及びそれを用いた複合部材

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002212749A (ja) * 2001-01-19 2002-07-31 Nippon Steel Corp 耐プレスかじり性と耐コイル変形性に優れた非クロメート型表面処理金属板及びその製造方法
JP2015080884A (ja) * 2013-10-22 2015-04-27 日新製鋼株式会社 複合体およびその製造方法、ならびに塗装金属素形材およびその製造方法
WO2015064689A1 (fr) * 2013-10-31 2015-05-07 株式会社神戸製鋼所 Plaque métallique traitée en surface et article moulé composite de plaque métallique-résine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11642871B2 (en) 2017-03-29 2023-05-09 Kobe Steel, Ltd. Surface-treated metal plate for polyolefin bonding, composite member, and method for manufacturing composite member
EP4035892A4 (fr) * 2019-09-26 2023-10-04 Toyobo Co., Ltd. Stratifié

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US20200316912A1 (en) 2020-10-08
CN108778716B (zh) 2021-05-11
JP2017170828A (ja) 2017-09-28
JP6621694B2 (ja) 2019-12-18
EP3434470A1 (fr) 2019-01-30
KR102142843B1 (ko) 2020-08-10
TWI630104B (zh) 2018-07-21
US11897230B2 (en) 2024-02-13
EP3434470B1 (fr) 2023-12-20
CN108778716A (zh) 2018-11-09
KR20180124964A (ko) 2018-11-21
TW201805165A (zh) 2018-02-16

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